Supersensitization of photographic emulsions containing planar cyanines



, 2,961,318 sce Patented Nov. 22, 1960 tolyl, chlorophenyl, etc., (e.g., a mononuclear aromatic 2,961,318 group of the benzene series containing from 6 to 7 carbon atoms), n and q each represents a positive integer of SUPERSENSITIZATION F PHOTOGRAPHIC from 1 to 2, d and m each represents a positive integer EMULSIONS CONTAINING PLANAR CY' 5 of from l to 3 (when a' is 3, R0 is always a hydrogen ANINES atom, and when m is 3, R2 is always a hydrogen atom),

Jean E. Jones, Rochester, N.Y., assignoito Eastman Q represents an oxygen atom, a divalent sulfur atom, or Kodak Company, Rochester, N.Y., a corporation of the non-metallic atoms necessary to complete a diazole New Jersey ring, e.g., Q is -NR- wherein R' is an alkyl group,

. f 10 -such as methyl, ethyl, propyl, etc. (e.g., an alkyl group Filed Sept' 30 1957 Ser'No' 687285 containing 'from 1 to 3 carbon atoms) or an aryl group,

Claims. (Cl. 96-104) such as phenyl, tolyl, etc. (e.g., a mononuclear aromatic group of the benzene series containing from 6 to 7 carbon atoms), or alternatively, Q represents the non-metallic taining planar, undissociated cyanine dyes, and in super- 15 atfmss necessafyfo 00111131016 a h ocycc 110010115 0011 sensitizing combination therewith, certain sulfonated comtammg at0ms 111 the 1101010050110 1mg (especmuy (11010 pounds- 4 of said atoms are carbon atoms and the riemaining Ii is known in the art of making photographie emu,1 atoms are sulfur or nitrogen atoms, eg., a diazine ring), sions that certain dyes of the cyanine class alter the sensiand Zand Z1 each represents 11,10 11011'111ets1110 'f1t0111s 1100' iiviiy of photographie emulsions of the geiaiin0 siiver 20 essary to compiete a heterocyclic nu'cleus containing from halide kind, when the dyes areincorporated in the emul- 5ht0 atolms in the heeI'OCYChC ring, Such :iis thosegf sion. Itis also known that the sensitization produced by t e t 1az00 senes (e'ga 'f111az01e 4'111011151 132010 a given dye varies somewhat with the type of emulsion in 100thy11111as010 4`P11e1111111az0105 51311011301111212010 45j which the dye is incorporated. Furthermore, the sensidlmethylthlamle 45'd1phenylth1az01e 4"(2t111011yn1111 iizatien of a giVen emuisien by a given dye may be azole, etc.), those of the benzothiazole series (e.g.,benzoaltered by Varying the cenditions in the emulsion. For thiazole, 4chlorobenzothiazole, 5-chlorobenzothiazole, 6- example, the sensitization may be increased by increasing Chlorobnzothmzole 7'011101'000112001132010 4'1110015'1' the silver ion concentration or decreasing the hydrogen 001120111102010 S'methyibenzotmaze 6me111y11e11z01111 ion concentration (i.e., increasing the alkalinity) or both. azole 5'br0m0b011z0t111sz01e 6'1101110101120111132010 4' Thus, sensitization can be increased by bathing plates, ,Phe11y1bfs11z0th1az01e 5P11e11y1bs11z0t111a201e 441100101157 coated with a spectrally sensitized emulsion, in water or bef1z0t111az01ey 5meh0XbCIlZ0thlaZ 0le 6-metlioxybenzoin aqueous Solutions of ammonia. Such a process of `thiazole, S-iodobenzothiazole, 6,-1odibenzothiazole, 4- altering the sensitivity of a sensitized emulsion by increas- 01110715001120111132010 .5'611101313611201111212016 tetfahlfdfo ing the silver ion concentration and/ or by decreasing the benzoth1az0'10 5 6'01me1110Xybe11Z0t11132010 56010713" hydrogen ion concentration is commonly called hypen 35 methylenebenzothiazole, S-hydroxybenzothiazole, 6-hy- This invention relates to photographic emulsions coni j, i h en au droxybenzothiazole, etc.), those of the naphthothiazole gsltizilog qullsrensmzed emu sions ave g er y series (e.g., a-naphthothiazole (i.e., [2,1lnaphthothia- I have now found another means of altering the sensi 2010) 11aP11t1101111aZ01e (1-0" uimnaphthothlazok), 5'

methoXy--naphthothiazole, 5ethoxy--naphthothiazole, 40 7-methox -a-na hthothiazole -methoXy--naphthothianine dyes. Since the conditions in the emulsions, 1.e., y p l l the hydrogen ion and/or silver ion concentrations, under- 101?, etc-)i t1105,@ 0f the th1anaphtheno-7, ,6, ,4,5-th'iazole go little er no change in my method, I Shall designate series (e.g., 4 -methoxythianaphtheno-7 ,6 ,4,5-thiazole, my method as a kind of supersensitization etc.), those of the oxazole series (e.g., 4-methyloxazole, It is, therefore, an object of my invention to provide 5`methY10XaZ01e, 4-1511'6I1yl0XaZ01e, 4,5-d1phenyloxazole, photographic emulsions containing planar `dyes and, in 4'et1'1y10xaz01e 45'0111100151011212010 5'P11e11y10xaz01e supersensitizing combination therewith, certain sulfonated 010-), t110se 0f ,t110be11Z0XaZ010-s01`10s (eg', 0011201132010 compounds. Another object is to provide methods for 5 0111010001120732010 5 'Pheny10e11z0xas01e 5 11101115'1 making these emulsions. Other objects will become ,061120132010 0'1110111310011201132010 5601111001311301120110 apparent from a Consideration of the following descrip zole, 4,6-dimethylbenzoxazole, 5-methoxybenzoxazole, 6- tion and examples methoxybenzoxazole, S-ethoxybenzoxazole, 6-chlorobenz- The planar, undissociated cyanine dyes useful in prac- OXaZOle, 5hYdf0XYbef120XaZ01, 6hy( 10XYbeIlZ0XaZ0le ticing my invention can be advantageously represented etc-)i those 0f the IlaPh'fhOXaZOle SerleS (6%, vL-DaPh by the following general formula: thoxazole, -naphthoxazole, etc.), those of the selenazole tivity in photographic emulsions containing planar cyawherein R and R1 each represents an alcohol radical, i.e., series (e.g., 4-methylselenazole, 4-phenylselenazole, etc.), an alkyl group (substituted or unsubstituted), such as those of the benzoselenazole series (e.g., benzoselenazole, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n- S-chlorobenzoselenazole, 5methoxybenzoselenazole, 5- amyl, carboxymethyl, -carboXyethyl, carbomethoxyhyd roxybenzoselenazole, tetrahydrobenzoselenazole, methyl, carbethoxymethyl, -methoxyethyl, vinylmethyl etc.), those of the naphthoselenazole series (e.g., oc-naph- (allyl), phenylmethyl (benzyl), etc., (e.g., an alkyl group thoselenazole, -naphthoselenazole, etc.), those of the of the formula CHI-Ignirl wherein n represents a positive thiazoline series (e.g., thiazoline, 4-methylthiazoline, integer of from 1 to 4), R0 and R2 each represents a 70 etc.), those'of the 2-quinoline series (e.g., quinoline, 3- hydrogen atom, a lower alkyl group, such as methyl, methylquinoline, S-methylquinoline, 7-methylquinoline, ethyl, propyl, etc. (e.g., an alkyl group containing from 8-methylquiuoline, 6-chloroquinoline, 8-chloroquinoline, 1 to 3 carbon atoms), or an aryl group, such as phenyl, G-methoxyquinoline, -ethoxyquinoline, 6hydroxyquino-` "Qll wherein R, R1, d, m, Q, Z and Z1 each have the values ,given above.

The sulfonated derivatives useful in practicing my invention comprise polynuclear aromatic compounds containing at least one sulfo group. The term polynuclear aromatic as used herein is intended to mean 2 or more benzene rings fused together (for example, as in naphthalene, pyrene, etc.) or at least 2 benzene rings or aromatic rings directly joined together (for example, as in ,diphenyL terphenyl, quaterphenyl, etc.) or through an aliphatic linkage. veniently be represented by the following general formula:

Such sulfonated derivatives can conwherein R3 represents a polynuclear aromatic group as defined above and M represents a hydrogen atom or a water-soluble cation salt group (e.g., sodium, potassium, ammonium, triethylammonium, triethanolammonium, pyridinium, etc.). Among the most useful of the sulfonated derivatives embraced by Formula II above are the compounds represented by the following general formula:

SOSM

wherein B1 represents a 2-benzotriazolyl group or a 1,3,5- tnazln--ylamino group, B2 represents an aromatic group v(i.e. benzene or substituted benzene) and M has the v values given above. l

Typical of the sulfonated derivatives of Formula Ill above, wherein B1 represents a 1,3,5-triazin-6-ylamino group (i.e., a 1,3,5-triazin-2-ylamino group) are the com- -pounds selected from those represented by the following general formula:

wherein M has the values given above and R4, R5, Re,

R7 each represents a hydrogen atom or a substituent group, such as hydroxyl, aryloxyl (e.g., phenoxyl, o-toloxyl, p-sulfophenoxyl, etc.), alkoxyl (e.g., methoxyl, ethoxyl, etc.), a halogen atom (e.g., chlorine, bromine, etc.), a heterocyclic radical (e.g., morpholinyl, piperidyl, etc.), an alkylthio group (e.g., methylthio, ethylthio, etc.), an arylthio group (e.g., phenylthio, tolylthio, etc.), a heterocyclylthio group (e.g., benzothiazylthio, etc.), an

amino group, an alkylamino group (e.g., methylamino, ethylamino, propylamino, dimethylamino, diethylamino, dodecylamino, cyclohexylamino, -hydroxyethylamino, di--hydroxyethylamino, -sulfoethylamino, etc.), an arylamino group (e.g., anilino, o, m, and p-sulfoanilino, o, m, and p-chloroanilino, o, m, and p-anisylamino, o, m, and p-toludino, o, m, and p-carboxyanilino, hydroxyanilino, sulfonaphthylamino, o, m, and p-aminoanilino, p-acetamidoanilino, etc.), etc.

Compounds of Formula Illa wherein R4, R5, Re and/or R7 each represents a heterocyclylamino group (e.g., 2- benzothiazoleamino, Z-pyridylamino, etc.) can also be used in practicing my invention.

Another group of sulfonated derivatives which are useful in practicing my invention are those represented by the following general formula:

o Iv. Ogs

Rg RII R10 Rio lwherein RB is an acylamido group (e.g., acetamido, sulfobenzamido, 4-methoxy-3-sulfobenzamido, 2-ethoxybenzamido, 2,4-diethoxy, benzamido, p-tolylarnido, 4-methyl- 2methoxybenzamido, l-naphthoylamino, 2-naphthoylamino, 2,4-dimethoxybenzamido, 2-phenylbenzamido, 2- thienylbenzamido) or a sulfo group, R9 represents an acylamido group (e.g., as defined by R8 above), or a sulfoaryl group (e.g., sulfophenyl, p'sulfodiphenyl, etc.) and R10 represents a hydrogen atom or a sulfo group, said compound containing at least one sulfo group.

The planar, undissociated cyanine dyes useful in practicing my invention can be prepared according to the methods described in Heseltine and Brooker U.S. appli- `cation Serial No. 607,236, led August 30, 1956, now

U.S. Patent 2,927,026, issued March 1, 1960.

Compounds of Formula IIIa which can advantageously be employed in practicing my invention have been described in one or more of the following representative patents:

2,171,427 August 29, 1939 2,473,475 June 14, 1949 2,595,030 April 29, 1952 2,660,578 November 24, 1953 British:

595,065 November 26, 1947 623,849 May 24, 1949 624,051 May 26, 1949 624,052 May 26, 1949 678,291 September 3, 1952 681,642 October 29, 1952 705,406 March 10, 1954 The products of Formula Illa have been previously employed in the textile field, and are sold under such trade names as Leucophor B, Calcoiluor White MR, Tinopal (SP, WR, BV277, 2B, GS, NG), Blancofor SC, Hiltamine (BSP, N, Sol., 6T6), and the like.

The preparation of a number of compounds employed by Formula Illa above has been previously described in the copending application Serial No. 540,052 of B. H. Carroll, J. E. Jones, and l. Spence, tiled October 12, 1955, now U.S. Patent 2,945,762, issued July 19, 1960.

The dibenzothiophenedioxide compounds of Formula IV have, in general, been previously described in the prior art. See, for example, U.S. Patents 2,573,652; 2,580,234; and 2,563,493. Further examples of the preparation of such compounds are given in the copending application of l. E. Jones, J. Spence, and J. A. Van Allan, Serial No. 575,160, filed March 30, 1956, now U.S. Patent 2,937,089, issued May 17, 1960. Other cxamples. of` sulfonated derivatives embraced byFormula anemia II above `which can ladvantageously be used in lmy invention can be prepared according to the methods described in application Serial No. 575,160. Other examples of compounds represented by Formula II above which can be used in my invention have been previously described iu the copending application of B. H. Carroll, J. E. Jones, and J. Spence, Serial No. 540,054, iiled October 12, 1955, now U.S. Patent 2,950,196, issued August 23, 1960. (See, in particular, the compounds of Formulas II, III and IV of that application.)

Compounds selected from those of Formula III above wherein B1 represents a 2-benzotriazo1y1 group can be prepared according to methods previously described in the prior art. See, for example, U.S. patent to Zweidler et al. 2,713,057, dated July 12, 1955; Keller et al., U.S. Patent 2,684,966, dated July 27, 1954; Zweidler et al., U.S. Patent 2,784,197, dated March 5, 1957; and Keller et al., U.S. Patent 2,784,183, dated March 5, 1957. A somewhat related group of compounds containing a 2- benzotriazolyl group which can be used in my invention have been previously described in U.S. Patent 2,733,165. Such compounds are embraced by Formula II above.

Typical sulfonated derivatives embraced by Formulas II, III, IIIa and IV above are (chemical formulas are given for various types to aid in identification):

(1) A sulfonated triazolostilbene, e.g., of the type shown in U.S. Patent 2,713,057.

Bo wrm-@CILQH-@NH oH N soin Sloan N OH H 4,4di 4 ,6"-dihydroxy-Z"-s-triazinylamino) stilb ene-2,2'-

disulfonic acid.

sOiNa 5-methoxy-2(4-styryl-3-sulfo)phenyl-1,2,3 benzotriazole sodium salt. (11) Calcofluor White-MR, a sulfonated triazinyl stilbene.

CHQO

N Ho oHiCHi-NIP -NH@ A M M 2m p-quaterphenyl-4,4"-disulfonic acid.

SOaNa chrysene--sulfonic acid sodium salt.

SOaNB pyrene-S-sulfonic acid sodium salt.

(18) Phenanthrene3sulfonic acid sodium salt. l

( 19) 2,3-dimethylnaphthalene-1sulfonic acid sodium salt.

N Hof mimimrm N-o11 W, l N l Y NH IIH soaH 03H 2,8-bis[4(4-sulfoanilno)6-hydroxy-s-triazin-Z-ylamino] carbazole. Y

22 HOZNYNH@ \/N SOaH NH HQCHQOH NH-CHzCHr-OH N soia soin (28) S OzNa 4-sulfo-o-terphenyl sodium salt. (Jour. Organ. Chem.,

vol. 14 (1949), pg. 163.)

SOsNn pyrene-S-(4-methoxy-3-sulfostyryl)ketone sodium salt. (30) 3,7-bis(4-methyl-Z-methoxybenzamido)-2,8disulfodibenzothiophene-5,5-dioxide sodium salt.

As can be seen above, many of the sulfonated derivatives are employed in the form of their water-soluble salts, such as alkali metal (e.g., sodium, potassium, etc.) salts, or ammonium or amine (e.g., triethylamine, triethanolamine, pyridine, aniline, etc.) salts. By thus using these derivatives, they can be added to the emulsions in substantially neutral aqueous solutions without disturbing the pH of the emulsions.

According to my invention, I incorporate one or more of the planar dyes selected from those represented by Formula I (or la) above with one or more of the sulfonated derivatives of the type described above in a photographic emulsion. My invention is particularly directed to the ordinarily employed gelatino-silver-halide emulsions. However, my supersensitizing combinations can be employed in silver halide emulsions in which the carrier is other than gelatin, e.g., -a resinous substance or cellulose material which has no deteriorating etfect on the silver halides.

The planar dyes and sulfonated derivatives can be employed in various concentrations depending upon the effects desired. As is well known in the art, the sensitivity conferred upon an emulsion by a sensitizing dye does not increase proportionately to the concentration of the dye in the emulsion, but rather passes through a maximum as the concentration is increased. In practicing my invention, the planar dyes are advantageously employed in a concentration approximating their optimum concentration (i.e., the concentration at which the dye gives greatest sensitivity). In general, the sulfonated derivatives employed in my invention have little or no sensitizing action in the emulsions employed.

The optimum concentration of an individual sensitizing dye can be determined in a manner well known to those skilled in the art by measuring the sensitivity of a series of test portions of the same emulsion, each portion containing a different portion of the sensitizing dye. The optimum concentration of the planar dyes used in my invention can, of course, be readily determined in the same manner by measuring the sensitivity of a series of test portions of the emulsion, each portion containing a different concentration of the planar dye to be used in the combination. In determining the optimum concentration for the supersensitizing combination, it is advantageous 8 to employ at rst a concentration of the planar dye less than its optimum concentration, and then gradually increase the concentration of the dye until its optimum concentration is determined.

Ordinarily, the optimum or near optimum concentration of the planar dyes useful in practicing my invention is of the order of from 0.02 to 0.3 g. per mole of silver halide in the emulsion.

The sulfonated derivatives useful in practicing my invention can advantageously be employed in concentrations on the order of from 0.02 to 10.0 g. per mole of silver halide in the emulsion.

Generally speaking, the ratio of concentration of the complex cyanine dye to the sulfonated derivative can vary rather widely in my combinations, e.g., from 1:100 to 1:1 (by weight) in many instances.

The methods of incorporating sensitizing dyes in emulsions are well known to those skilled in the art, and as mentioned above, the sulfonated derivatives of my invention can be incorporated in the emulsions conveniently in substantially neutral aqueous solution. In practicing my invention, the planar dyes and sulfonated derivatives can be incorporated in the emulsions separately or together. Frequently, it is convenient to add the planar dyes and sulfonated derivatives separately in the form of solutions in appropriate solvents. Methanol, ethanol, pyridine, etc., have proven satisfactory as solvents for the planar dyes which I employ in my invention, although acetone has also been found to be satisfactory in certain cases. If desired, a mixture of solvents, such as methanol and pyridine, can be employed. The planar dyes and sul- `fonated derivatives can be added to the emulsions in any given order. The planar dyes and sulfonated derivatives are advantageously incorporated in the finished, washed emulsions and should be uniformly distributed throughout the emulsions. The following procedure is satisfacv tory: Stock solutions of the dyes and sulfonated derivatives desired are prepared by dissolving the same in appropriate solvents as described above. Then, `to the Howable gelatino-silver-halide emulsion, the desired amounts of the stock solution of one of the dyes (or sulfonated derivatives) is slowly added, while stirring the emulsion. Stirring is continued until the dye is thoroughly incorporated in the emulsion. Then, the desired amount of the stock solution of the sulfonated derivative (or dye, if sulfonated derivative has been added rst) is slowly added to the emulsion, while stirring. Stir-ring is continued until the second ingredient is thoroughly incorporated. The supersensitized emulsion can then be coated out on a suitable support, such as glass, cellulose derivative lm, resin film, or paper, to a suitable thickness and allowed to dry. The details of such coating methods are well known to those skilled in the art.

The amounts of the planar dyes and sulfonated derivatives actually incorporated in the emulsion will vary somewhat from case to case, according to the emulsion employed and according to the effect desired. The regulation and adoption of the most economical and useful proportions will be apparent to those skilled in the art upon making the ordinary observations and tests customarily employed in the art. Accordingly, the foregoing procedures and proportions are to be regarded only as illustrative. Clearly, my invention is directed to any emulsion containing a combination of the aforesaid planar dyes and sulfonated derivatives whereby a supersensitizing effect is obtained.

My invention is primarily directed to the ordinarily employed gelatine-silver-halide developing-out emulsions, e.g., gelatino-silver-chloride, chlorobromide, -chloroiodide, chlorobromiodide, -bromide and -bromiodide developing-out emulsions. While the results in the following table were obtained using gelatino-silver-bromiodide emulsions, excellent results have also been obtained using gelatino silver chlorobromide emulsions. Emulsions which form the latent image mostly inside the silver "9 halide grains, such as the emulsions set forth lin U.S.' Patent 2,456,956, dated December 21, 1948, can also be employed in practicing my invention.

Photographic silver halide emulsions, such as those listed above, containing the supersensitizing combinations of my invention can also contain such addenda as chemical sensitizers, e.g., sulfur sensitizers (e.g., allyl thiocarbamide, thiourea, allylisothiocyanate, cystine, etc.), various gold compounds (e.g. potassium chloroaurate, auric trichloride, etc.) (see U.S. Patents 2,540,- 085,; 2,597,856; and 2,597,915), various palladium compounds, such as palladium chloride (U.S. 2,540,086),

potassium chloropalladate (U.S. 2,598,079), etc., or mix- Y' tures of such sensitizers; antifoggants, such as ammonium chloroplatinate (U.S. 2,566,245), ammonium chloroplatinite (U.S. 2,566,263),"benzo'triazole, nitrobenzimidazole, S-nitroindazole, benzidine, mercaptans, etc. (see Mees, The Theory of the Photographic Process, Macmillan Pub., 1942, page 460), lor mixtures'thereof; hardeners, such as formaldehyde (U.S. 1,763,533), .chrome as those described in U.S. Patent 2,423,730, Spence vand Carroll U.S. Patent 2,640,776, issued June 2, 1953, etc.;V

or mixtures of such addenda. Dispersing agents for given above. Especially useful dyesv represented by Formulas I, Ia, V or Va are those dyes wherein d and m` represent a positive integer of from 1 to 2, and more Y particularly where either d or m is 2. In some `in- 5 stances, dyes, where both d and m represent 1, do not provide the unique effects illustrated below for Vdyes wherein d or m is 2.

The following examples will serve to illustrate further the manner of practicing my invention. To different portions of the same batch of photographic gelatine-silverbromiodde emulsion wereadded (l) a planar dye of Formulas I, la, V or Va and (2) a combination of the planar dye and asulfonated derivative as described above.- Before coating, the emulsions containing the addenda were digested for a short time (about l0 minutes) ina tank maintained at approximately 50 C. The different portions of emulsion were then coated on conventional supports (glass or cellulose ester film) and exposed in the usual manner in a spectograph and Eastman Type Ib .20 ,Sensitometer through a Wratten No. 12 Filter, i.e., a filter alum (U.S. 1,763,533), glyoxal (U.S. 1,870,354), dibromacrolein (Br. 406,750), etc.; color couplers, suchY which transmits substantially no light of wavelengths V.shorter than about 495 mp. (except for about 1% between 300 and 340 ma). The exposed coatings were then processed lfor 3 minutes in a developer having the follow- V ing composition:

color couplers, such as those set forth in U.S. Patents G. 2,322,027 and 2,304,940, can also beV employed in the N-rnethyl-p-aminophenolsulfate 2.0 abovedescribed emulsions. Y Hydroquinone 8 0 Another groupv of planar dyes which can advanta- Sodium sulfite (anhydrous) 90.0 geously be employed in supersensitizing combination Sodium carbonate (monohydrate) 52.5 with the sulfonated derivatives of my invention include Potassium bromide 5.0

the dyes represented by the following general formula:

O RII v("J-.ILT R.

Water to make one liter.

wherein R, n, d, m, q, Q, Z, R0, R2 and Z1 each have the` values given above, R represents an alkyl group, such as methyl, ethyl, n-propyl, vinylmethyl (allyl), etc., and J represents a nitrogen atom or a methine group. These planar dyes can advantageously be prepared by heating in the presence of an alkali, or organic amine, complex cyanine dyes (which have Rl-X- attached to the nitrogen atom of the heterocyclic nucleus defined by Z1). This method is well known to those skilled in the art and is illustrated in several ofthe examples below. `Particularly l useful planar dyes embraced by Formula V are those dyes represented by the following general formula:

As mentioned aobve, no data showing the sensitometric 4o properties of the sulfonated derivatives alone are given,

' 0 fog. It is to be noted that differences in speed are quite Va. l,2.` 0:(3- 1511-3" Y zu significant, Ysince a dilerence of 30 units represents a )d1 Q I l speed figures for the dyes alone have been adjusted to wherein R, R, d, m, J, Q, Z and Z1 each have the values be for purposes of comparison with the speeds for the supersensitized coatings, i.e., the speeds are relative. TABLE A ln'exactly the manner described above, the data'in Table B below were obtained. The only difference between the manner of recording the data is with respect to the speed figures, which are not on a relative basis as in the case of the data of Table A. The coatings of Examples 8-12 were obtained from the same hatch of emulsion; the coatings of Examples 13-14 were obtained from the same batch of emulsion; the coatings of Examples 24 and 25 were obtained from the same batch of emulsion, and the coatings of Examples 27-30 were obtained from the same batch of emulsion.

TABLE B 12 idene) ethylidene] 2 methylmercapto 2 thiazolin;` 4-one etho-p-toluene sulfonate and 1.4 g. of quinaldine was heated over a free ame for about 1 minute. The cool reaction mixture was stirred with 10 ml. of acetone. After chilling, the solid was collected on a filter and washed with acetone. The residue was suspended in 25 ml. of hot methyl alcohol and treated with an excess of triethylamine. The suspension was chilled, and the dye was collected on a lter and washed with methyl alcohol. The yield of dye was 48% crude and 25% after two recrystallizations from methyl alcohol. The red crystals Example Addenda (g./mol. AgX) Minus-Blue Light Exposure Speed Gammo Fog dye (n) (.08) plus compound 26 (.05)-

dye (n) (.08) plus compound l0 (.05).

dye (n) (.08) plus compound 27 (.05). dye (n) (.08) plus compound 13 (.05). dye (n) (.08 plus compound 15 (.0-5).-

dene)propenyl]1phen dye (t) (.08) plus compound 26 (.05)

dye (i) (.08) plus compound 27 (.05

dye (w) (.08) plus compound 10 (.05)

dye (w) (.08) plus compound 15 1) dye (e) (.08) plus compound 10 (.05)

dye (b) (.08) plus compound 13 dye (d') (.08) lus compound 26 (.05

{(k') dy (J') (.08) plus compound 10 05) (l) {(m) d e (l') (.08) plus compound 10 (.05

) dye (n) (.08)!plus compound 11 (.05)

5-(3-ethyl2(3 thiazolin-ft-one (.08).

-benmthiazo1y1idene)-24(3ethy1-2 (sm-benzotmamlyudene) prfiy' dye (q') (.08) gus compound 11 (.0

dye (3') (.08) plus compound 10 (.05)

dye (a) t 08) dye (a) (ifplus compound 16 (0.64).Y dye (a) (.08) plus compound 28 (0.04 dye (a) (.08) plus compound thiazolidinonc (.08).

l www on wvcauono oownouxo dye (y') (.os) plus cdmpound 11 thinzolidiuone (.08)

(b") dye (o") (.08) plus compound 11 (.05

thiazoldnone (.05). (d") dye (c) (.08) plus compound 11 (.05)

As indicated above, the dyes represented by Formula I can be prepared according to the method described in 60 V copending application 607,236. The following examples will illustrate the method of making dyes represented by p Formula V above.

A mixture of 2.6 g. of 5-[(3-ethyl-2(3H)benzoxazolylidene) ethylidene] 2 methylmercapto 2 thiazolin-4-one ethoptoluenesulfonate and 1.43 g. of lepidine was `heated over a free ame for about 1 minute. The cool reaction mixture was stirred with 10 ml. of acetone.

After chilling, the solid lwas collected on a rfilter and washed with acetone. The residue was suspended in 15 ml. of hot methyl alcohol and treated with an excess of triethylamine. The suspension Was chilled and the dye was collected on a filter and washed with methyl alcohol. The yield of dye was 12% crude and 7% after two recrystallizations from methyl alcohol. The reddish crystals melted at 2l2-213 C. with decomposition.

A mixture of 1.2 g. of -[(3-ethyl-2(3H)benzoxazol ylidene) ethylidene] 2 met-hylmercapto 2 thiazol-in-4-one etho-p-toluene sulfonate, 0.34 g. of 2-aminobenzoxazole, 0.25 g. of triethylamine and 20 ml. of anhydrous ethyl alcohol was heated, with shaking, at the refluxing temperature for 5 minutes. The reaction mixture was chilled and the solid was collected on a filter and washed with methyl alcohol. The yield of dye was 37% crude and 5% after three recrystallizations from methyl alcohol. The orange crystals melted at 253-254" C. with decomposition.

Listed below are the melting points of several of the dyes of my invention, which were obtained according to the method described in application Serial No. 607,236.

Melting Point, Dye C. with decomposition While it is to be understood that several of the dyes of my invention were added to the silver halide emulsions in the form of their acid addition salts, it is well known that such dyes do not exist in the emulsions in the form of their acid addition salts, rather they exist in the dye form,

such as is illustrated by Formula I above. yIt is, therefore, to be understood that the formulas in the foregoing specification and in the following claims, contemplate the addition to the emulsions of either the free dyes or their v acid addition salts.

The term sulfo as used in the foregoing specification and in the following claims means the free sulfonic acid group, as well as water-soluble salts of this group, such as sodium, potassium, ammonium, organic ammonium,

etc.

The accompanying drawing illustrates the supersensitizing effect obtained with three of my new combinations i of dyes in an ordinary gelatino-silver-bromiodide emulsion. Each ligure of the drawing is a diagrammatic reproduction of two spectrograms. In each figure, the sensitivity of the emulsion containing only the complex dye of Formula I or Ia is illustrated by the solid curve. The

uppermost curve (broken line), represents the sensitivity p conferred upon the emulsion by a combination of the dye of Formula I yor Ia and a sulfo compound, such as one from the group represented by those of Formula II. No curve representing the effect on the emulsion of the sulfo compound alone is given, inasmuch as it has been found that these have little or no measurable effect on the sensitivity of ordinary silver halide emulsions.

In Figure l., curve A represents the sensitivity of an ordinary gelatino-silver-bromiodide emu'sion sensitized with 3 ethyl 5 [(.3 ethyl 2(3H) benzoxazolylidene)ethylidene] 2 [(2 quinolyl)methylene] 4- thiazolidinone while curve B represents the sensitivity of the same emulsion containing 3-ethyl-5[(3-ethyl 2(3H) benzoxazolylidene)ethylidene] 2 [(2 quin- 0lyl)methylene]-4-thiazolidinone, and a diaminostilbenedisulfonate ,such as Calcouor White-MR. The sensi tometric characteristics of these coatings are given in Example 33 of the above table.

In Figure 2, curve C represents the sensitivity of an ordinary gelatine-silver-bromiodide emulsion sensitized with 1 phenyl 5 [(1,3,3 trimethyl 2(3H) -indolylidene)ethylidenel 2 [3 (1,3,3 trimethyl 2(3H)- indolylidene)propenyll 4,6( 1II,5H) pyrimidinedione while curve D represents the sensitivity of the same emulsion sensitized with 1-phenyl-5-[(l,3,3trimethyl-2(3H)- indolylidene)ethylidene] 2 [3 (1,3,3 trimethyl- 2(3H) indolylidene)propenyl] 4,6( 1H,5H) pyrimidinedione and 5 acetamido 2 (4 styryl 3 sulfo) phenyl-1,2,3-benzotriazole sodium salt. The sensitometric measurements for these emulsions are given in Example 8 of the above table.

In Figure 3, curve E represents the sensitivity of an ordinary gelatino-silver-bromiodide emulsion sensitized with 3 [(3 ethyl 2(3H) benzothiazolylidene)ethylidene] 7 [(3 methyl 2(3H) benzothiazolylidene) methyl]imidazo[1,2,alpyridin 2(3H) one While curve F represents the sensitivity of the same emulsion sensitized with 3 [(3 -ethyl- 2(3H) benzothiazolylidene) ethylidene] 7 [(3 methyl 2(3H) benzothiazolylidene)methyl]imidazo[1,2-alpyridin 2(3H) one and 3,7 bis(2 phenylbenzamido) 2,8 -disulfodibenzothiophene-5,5dioxide sodium salt. The sensitometric measurements for these emulsions are given in Example 20 of the above table.

What I claim as my invention and desire secured by Letters Patent of the United States is:

l. A photographic silver halide emulsion sensitized with a supersensitizing combination of (a) at least one planar, undissociated dye selected from those represented by the following general formula:

wherein R and R1 each represents an alkyl group, R0 and R2 each represents a member selected from the group consisting of a hydrogen atom, a lower alkyl group, and

an aryl group, n, d, m and q each represents a positive integer of from 1 to 2, Q represents a member selected `from the group consisting of an oxygen atom, a divalent sulfur atom, the non-metallic atoms necessary to complete a diazole ring, and the non-metallic atoms necessary to complete a diazine ring, and Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the th-iazole series, those ofthe benzothiazole series, those of the naphthothiazole series, those of the benzoxazole series, those of the naphthoxazole series, those of 15 consisting of (A) a carbocyclic compound selected from those represented by the following general formula:

(2) D-SO3H wherein D represents an aromatic group comprising an aromatic ring selected from the class consisting of a biphenyl ring, a terphenyl ring, a quaterphenyl ring, and an aromatic group containing at least two benzene rings fused together, (B) a water-soluble salt of a compound ,represented by said Formula 2, (C) a dibenzothiophene dioxide compound selected from those represented by the following general formula:

R Rg

`wherein R8 represents a member selected from the group consisting of acylamido group and a sulfo group, R9 represents a member selected from the group consisting of an acylamido group and a sulfoaryl group, and R10 represents a member selected from the group consisting of a hydrogen atom and a sulfo group, said Compound ,3 containing at least one sulfo group, and (D) a compound selected from those represented by the following general formula:

SOeM

wherein B1 represents a member selected from the group consisting of a 2-benzotriazolyl group and a 1,3,5-triazin- -ylamino group, B2 represents an aromatic group, and M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom.

42. A photographic gelatino-silver-halide developingout emulsion sensitized with a supersensitizing combination of (a) at least one planar, undissociated dye selected from those represented by the following general formula:

wherein R and R1 each represents an alkyl group containing from 1 to 2 carbon atoms, d and m each represents a positive integer of l to 2, provided that both d and m do not simultaneously represent l, Q represents a member selected from the group consisting of an oxygen one nucleus and the non-metallic atoms necessary to complete a pyrimidinedione nucleus, and Z and Z1 each represents the nonmetallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the thiazole series, those of the benzothiazole series, those of the benzoxazole series, those of the naphthoxazole series, those of the benzoselenazole series, those of the 2-quinoline series, and those of the 3.3-dialkylindolenine series, and (b) at least one water-soluble compound, containing at least one sulfo group, selected from the class consisting of (A) a carbocyclic compound selected from those represented by the following general formula:

(2) D so3H wherein D represents an aromatic group comprising an aromatic ring selected from the class consisting of a biphenyl ring, a terphenyl ring, a quaterphenyl ring, and an aromatic group containing at least two benzene rings fused together, (B) a water-soluble salt of a compound represented by said Formula 2, (C) a dibenzothiophene "16 dioxide compound selected from those represented by the following general formula: (3) 0\ R SOJM wherein B1 represents a member selected from the group consisting of a Z-benzotriazolyl group and a 1,3,5-tri- I azin6ylamino group, B2 represents an aromatic group,

(atom, a divalent sulfur atom, the non-metallic atoms Y necessary to complete an imidazoE1,2a]pyridin-(2,3H)

and M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom.

3. A photographic emulsion as defined in claim 2 wherein the silver halide is silver bromiodide.

4. A photographic gelatino-silver-halide developingout emulsion sensitized with a supersensitizing combination of (a) at least one planar, undissociated dye selected from those represented by the following general formula:

wherein R and R1 each represents an alkyl group containing from l t0 2 carbon atoms, d and m each represents a positive integer of from l to 2, provided that both d and m do not simultaneously represent 1, Q represents a member selected from the group consisting of an oxygen atom, a divalent sulfur atom, the nonmetallic atoms necessary to complete an imidazo[l,2-a]pyridin-(2,3H) one nucleus and the non-metallic atoms necessary to complete a pyrimidinedione nucleus, and Z and Z1 each represents the nonmetallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the thiazole series, those of the benzothiazole series, those of the benzoxazole series, those of the naphthoxazole series, those of the benzoselenazole series, those of the 2-quinoline series, and those of the 3,3-dialkylindolenine series, and (b) at least one water-soluble compound selected from those represented by the following general formula:

SOsM

wherein B1 represents a member selected from the group cons1st1ng of a Z-benzotriazolyl group and a 1,3,5-triazinp-ylamino group, B2 represents an aromatic group, and

wherein R and R1 each represents an alkyl group contaimng from 1 to 2 carbon atoms, d and m each represents a positive integer of from 1 to 2,'provided that both d and m do not simultaneously represent 1, Q-represents a member selected fro mthe group consisting of an oxygen atom, a divalent sulfur atom, the nonmetallic atoms necessaryeto complete an imidazo[1,2-a]pyridin-(2,3H) one nucleus and the non-metallic atoms necessary to complete a pyrimidinedione nucleus, and Z and Z1 each represents the nonmetallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the thiazone series, those of the benzothiazole series, those of the benzoxazole series, those of the naphthoxazole series, those of the benzoselenazole series, those of the 2-quinoline series, and those of the 3,3-dialkylindolenine series, and (b) at least one water-soluble compound selected from those represented by the following general formula:

-containing at least one sulfo group.l

6. A photographic silver halide emulsion sensitized with a supersensitizing combination of (a) at least one planar, undissociated dye selected from those represented by the following general formula:

wherein R and R1 each represents an alkyl group containing from 1 to 2 carbon atoms, d and m each repreh sents a positive integer lof from l to 2, provided that both d and m do not simultaneously; represent 1, Q represents a member selected from ,theV group consisting of an oxygen atom, a divalent sulfur atom, the nonmetallicatoms necessary to complete an imidazoil,2-a]PY1idin-(2,3H) one nucleus, and the non-metallic atoms lnecessary to complete a pyrimidinedione nucleus, and Z and Z1 each represents the non-metallic katoms necessary to complete a heterocyclic nucleus of the benzothiazole series, and (b) at least one water-soluble compound, containing at least one sulfo group, selected from the class consisting or" (A) a carbocyclic compound `,selected from those represented by the following general formula' l (2') Y' DsomVVV f p wherein D represents an aromatic group comprising an aromatic ring selected fromthe class consisting' of a biphenyl ring, va terphenylring, a quaterphenyl 'ring and an aromatic group containing A at least two benzene rings fused together,` (B) a water-soluble salt of a compound represented by said Formula`2, (C) a'dibenzthiophe'ne dioxide ,compound selected -'from'those representedlby the following general formula;

wherein R8 represents a member selected from the group consisting of anacylamido group and a sulfo group, R9

3 containing at least one sulfo group, and (D) a coni--V pound selected from those represented by the following general formula: r

SOSM

wherein R and R1 each represents an ,alkyl group containing from l to 2 carbon atoms,d and meach represents a positive Iinteger of from l to 2, providedV thatboth d and m do not simultaneously represent A1, Q represents a member selected from the group consisting of an oxygen atom, a divalent sulfur atom,v the non-metallic atoms necessary to complete an imidazoll,2a]PYridin1,(2,3H) one nucleus, and the nondmetallic atoms necessaryto complete a pyrimidinedione nucleus, and Z and Z1 each represents the non-metallic atoms necessary t'complete a heterocyclic nucleus of the benzothiazole series, Sand '(b) at least one water-soluble compound selected from those represented by the following general'formula: n

CH=CH-B2 SOsM wherein B1 represents a member selected from the group consisting of a Z-benzotriazolyl group and a 1,3,5-triazin- -ylamino group, B2 'represents an aromatic group, and M represents a mem-ber selected from the group consisting of a hydrogen atom and an kalkali'metal atom.

8. A photographic silver halide emulsion sensitized with ya supersensitizing combinationV of (a) at least;l one planar, undissociated dye selected from those represented by the following general formula:

I i |ioH(=oHoH)m1=--\t-R1 Y "Qs ,n wherein R and R1 each represents an alkylgr'oup con,- taining from 1 to 2 carbon atoms, d and m each repre sents a positive integer offrorn l to 2, provided that both d and m do not simultaneously represent 1, Q represents a member selected from the group consisting of an oxygen atom, a divalent .sulfur ,.atom,` the non-metallicratoms necessary `to complete an imidazot 1,2-a] pyridin-(f2,3H),- one nucleus, and the non-metallic atoms necessaryfto complete a pyrimidinedione nucleus, and Z and Z1 each represents the non-metallic atoms necessary-to complete a heterocyclic nucleus of the benzothiazoleseries, and (b) at least one water-soluble compound selected from those represented by the following general rformula:V

wherein R8 represents a member selected fromthe group consisting of an acylamido group and a sulfo group, R5 represents a member selected from the grolltp'consisting t 19 v i t of an acylamido group and a sulfoaryl group, and RV represents a member selected from the group consisting of a hydrogen atom and a sulfo group, said Compound b containing at least one sulfo group.

9. A photographic silver halide emulsion sensitized with a supersensitizing combination of (a) at least one planar, undissociated dye selected from those represented by the following general formula:

`QI wherein R and R1 each represents an alkyl group containing from 1 to 2 carbon atoms, d and m each represents a positive integer of from 1 to 2, provided that both d and m do not simultaneously represent 1, Q represents a member selected from the group consisting of an oxygen atom, a,` divalent sulfur atom, the non-metallic atoms necessary to complete an imidazo[1,2-alpyridin-(2,3H) one nucleus, and the non-metallic atoms necessary to cornplete a pyrimidinedione nucleus, and Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the 2-quinoline series, and V(b) at least one water-soluble compound, containing at least one sulfo group, selected from the class consisting of (A) a carbocyclic compound selected from those represented by the following general formula:

(2) D-SO3H wherein D represents an aromatic group comprising an aromatic ring selected from the class consisting of a biphenyl ring, a terphenyl ring, a quaterphenyl ring, and an aromatic group containing at least two benzene rings fused together, (B) a water-soluble salt of a compound represented by said Formula 2, (C) a dibenzothiophene dioxide compound selected from those represented by the following general formula:

R Re

Rx Rio wherein R8 represents a member selected from the group consisting of an acylamido group and a sulfo group, R9 represents a member selected from the group consisting of an acylamido group and a sulfoaryl group, and R10 represents a member selected from the group consisting of a. hydrogen atom and a sulfo group, said Compound 3 containing at least one sulfo group, and (D) a compound selected from those represented by the following general formula:

20 a member selected from the group consisting of an oxygen atom, a divalent sulfur atom, the non-metallic atoms necessary to complete an imidazo[l,2-a]pyridin(2,3H) one nucleus, and thenon-metallic atoms necessary to complete a pyrimidin'edione nucleus, and Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the 2-quinoline series, and (b) at least one water-soluble compound selected from those represented by the following general formula:

SOaM wherein B1 represents a member selected from the group consisting of a 2-benzotriazolyl group and a 1,3,5-triazin 6-ylamino group, B2 represents an aromatic group, and M represents a member selected from the group consisting of a hydrogen atom and an alkali metal atom.

11. A photographic silver halide emulsion sensitized with a supersensitizing combination of (a) at least one planar, undissociated dye selected from those represented by the following general formula;

lz i Zh wherein R and R1 each represents an alkali group cone taining from 1 to to carbon atoms, d and m each repre sents a positive integer of from l to 2, provided both d and m do not simultaneously represent 1, Q represents the non-metallic atoms necessary to complete an imidazo` i1,2-a]pyridin-(2,3H)one nucleus, and Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series, and (b) atleast one water-soluble compound selected from' those represented by the following general formula:

S a n1 wherein R and R1 each represents an alkyl group containing from 1 to 2 carbon atoms, d and m each represents a positive integer of from 1 to 2, provided both d and m do not simultaneously represent 1, Q represents the non-metallic atoms necessary to complete a pyrimidinedione nucleus, and Z and Z1 each represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series, and (b) at least one water-soluble compound selected from those represented by the following general formula:

@erben-B1 B1 SOaM wherein B1 represents a member selected from the group 1 consisting of a 2benzotriazolyl group and a 1,3,5-triazinl 2,961,818 Y 2 1@ 22 '6-ylamino group, B1V represents an aromatic group, and M represents a member selected fromV the group consist- `ing of a hydrogenatom and an alkali metal atom.

v13. A photographic silver halide emulsion/sensitized 3-Sulfo)phenyl-1,2,3-benzotriazole'sodiumsalt cwith a supersensitizing combination of (a) at least one `17.v Alphotographic silver halideemulsion sensitized planar, undissociateddye selected from those represented with a supersensitizing combination comprising 5-[(1V bythe following general formula: i Y ethyl 2(1H) quinolylidene)ethylidene]-2-[3( l-ethyli l i i 2(1H) quinolylidene)propenyl]-l-phenyl4,6( lH,5H) Z\ 0= |3I ZM pyrimidinedione hydroiodide and 5-methoxy-2-(4-styryly `\T 3sulfo)phenyl-1,2,3-benzotriazole sodium salt. R N C( CH CHM l Q CH( OH CHM l C L Rx 18. A photographic silver halide emulsion sensitized `Q with a superse'nsitizing combination comprising ,3[(3' wherein R and R1 each represents an alkyl group C0I1 ethyl- 2(3H7) benzothiazolylidene)ethylidene] 7 [(3- tainirig from 1 to 2 Carbon atoms, d and m each reP're' methyl 2(3H) benzothiazolylidene)methyl]imidazof sente e positive integer of from 1 to 2, provided beth 15 i1,`2-aipyridin-2(3H)-dne` hydroiodide and 3,7-bis(2 d and m de not Simultaneously represent 1, Q represents phenyibenzamido)-zgs-disuifodibenzothiophene 5,5 iiithe non-metallic atoms necessary to complete a pyrimi- Oxide, dinedione Buelens, and Z and Z1 each represents the non- 19. A photographic silver halide emulsion sensitized metallic atoms necessary to eorniilete a heteroeyel'ie with a supersensitizing combination comprising 2-[(3 nucleus of the 2-quinoline series, and (b) at least one 20 ethy1-2(311) benzothiazdylidene)propenyl] 5 [(3. water-soluble compound selected from those represented ethyl 2(31-1) benzothiazolylidem)ethylidenejthiazolin. by the following general formnla 4-one and 5-methoxy2(4-styryl-3sulfo)phenyl1,2,3-

benzotriazole sodium salt. CH=CHBI 20. A photographic silver halide emulsion sensitized B1 25 with a supersensitizing combination of (a) at least one SOM planar, undissociated dye selected from those represented wherein B1 represents a member selected from the group by the following general formula:

consisting of a 2-benzotriazolyl group and a 1,3,5-triazin- 35 wherein R and R" each represents an alkyl group, R0 6-ylamino group, B2 represents an aromatic group, and and R2 each represents a member selected from the group M represents a member selected from the group consistconsisting of a hydrogen atom, a lower alkyl group, and ing of a hydrogen atom and an alkali metal atom. an aryl group, n, d, m and q each represents a positive 14. A photographic silver halide emulsion sensitized integer of from l to 2, Q represents a member selected with a supersensitizing combination of (a) at least one from the group Consisting of an oxygen atom, a dValent planar, undissociated dye selected from those represented sulfur atom, the non-metallic atoms necessary to comby the following general formula: plete a diazole ring, and the non-metallic atoms necessary to complete a diazine ring, and Z and Z1 each represents the non-metallic atoms necessary to complete a /Z`x` 0:? l: /Z"\ 45 heterooyclic nucleus selected from the group consisting of R-N--G(=CHCH)d-i=r2` IC-Ci(=CH-CH)m-1=o N-Ri those of the thiazole series, those of the benzothiazole ",s," series, those of the naphthothiazole series, those of the benzoxazole series, those of the naphthoxazole series, wherein R and Ri eaell represents en al-lyl group con' those of the benzoselenazole series, those of the naphthotaining frornl 1 to 2 Carbon atoms, d and m eaeh repre* 50 selenazole series, those of the Z-quinoline series, those of sents a Positive integer of from 1 to 2, Provided that bot-l1 the 4-quinoline series, and those of the 3,3-dialkyld and m d0 nOt Simultaneously represent 1, and Z and Z1 indolenine series, and (b) at lease one water-soluble comeach represents the nonmetallic atoms necessary to compound, Containing at least 011e sulfo group, selected from plete a heterocyclic nucleus of the benzothiazole series, the Class Consisting 0f (A) a carbocyclic compound seand (b) at least one Water-Soluble CornPOllnd Seleeted lected from those represented by the following general from those represented by the following general formula: formula;

(2) D-SO3H CH=CHB1 Q wherein D represents an aromatic group comprising an B* SlOaM aromatic ring selected from the class consisting of a biphenyl ring, a terphenyl ring, a quaterphenyl ring, and wherein B1 represents a member selected from the group an aromatic group containing at least two benzene rings consisting of a 2-benzotriazolyl group and a 1,3,5-triazinfused together, (B) a water-soluble salt of a compound -yllamino group, B2 represents an aromatic group, and represented by said Formula 2, (C) a dibenzothiophene M represents a member Selected from the group consist. dioxide compound selected from those represented by the ing of a hydrogen atom and an alkali metal atom. following general formula 15. A photographic silver halide emulsion sensitized (3) o O with a supersensitizing combination comprising 7[(3 ethyl 2(3H) benzothiazolylidene)propenyll 3 (3- R, S\ R, methyl-2(3H)-benzothiazolylidene)imidazo[1,2 alpyri- 70 din-2(3H)one hydroiodide and 3,7bis(4methy12 R1 R11 methoxybenzamido) 2,8 disulfodibenzothiophene 5,5-

dioxide sodium salt. wherein R8 represents a member selected from the group 16. A photographic silver halide emulsion sensitized consisting of an acylarnido group and a sulfo group, R9 with a supersensitizing combination comprising 5-[(3 75 represents a member selected from the group consisting of an aeylamido group and a sulfoarylA group, and R10 represents a member selected from the group consisting of a hydrogen atom and a sulfo group, said Compound 3 containing at least one sulfo group, and (D) a compound selected from those represented by the following general formula:

SOzM

References Cited in the file of this patent UNITED STATES PATENTS /W Mutscheuer sept. 9, 1919 Eggert et al. Ian. 9, 1940 Brooker Nov. 23, 1948 Anish Dec. 6, 1949 Murray` Dec. 12, 1950 Wolfson Sept. 20, 1955 FOREIGN PATENTS Germany Dec. 4, 1952 OTHER REFERENCES Clerc: Photography Theory and Practice, 3rd ed., p. 235, Pitman Pub. Corp., New York, 1954.

UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION Patent No, 2,261,318 November 22, 1960 Jean E., Jones It s hereby oertfed'that error appears in the above numbered patent requiring Correction and that Jfine said Letters Patent should read as corrected below.

signed and sealed ems zon@ day 01 June 1961.

(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents 

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION SENSITIZED WITH A SUPERSENSITIZING COMBINATION OF (A) AT LEAST ONE PLANAR, UNDISSOCIATED DYE SELECTED FROM THOSE REPRESENTED BY THE FOLLOWING GENERAL FORMULA: 